Pyridyloxy-phenoxy-alkanethiocarboxylic acid ester derivatives and their herbicidal use

ABSTRACT

Herbicidal and plant growth-regulating action. Pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula ##STR1## wherein A is cyano or carboxyl, an ester, thioester or amido radical or the salt of the carboxylic acid with a cation or a quaternary ammonium group, 
     Z is hydrogen, halogen, cyano, nitro, C 1  -C 4  alkyl or C 1  -C 4  alkoxy, 
     D is hydrogen, halogen, cyano, nitro or C 1  -C 4  alkoxy, 
     E is halogen, trifluoromethyl or cyano. 
     R 1  is hydrogen, C 1  -C 4  alkyl, C 2  -C 8  alkoxyalkyl or C 1  -C 5  alkoxy carbonyl and 
     R 2  is hydrogen or C 1  -C 4  alkyl.

CROSS-REFERENCE TO RELATED APPLICATION

This is a divisional of application Ser. No. 140,402 filed on Apr. 14,1980, now Pat. No. 4,329,167, which is a continuation-in-part ofapplication Ser. No. 080,965, filed on Oct. 1, 1979, now abandoned.Application Ser. No. 080,965 was a continuation of application Ser. No.919,119, filed on June 26, 1978, now abandoned.

DETAILED DISCLOSURE Pyridyloxy-Phenoxyalkanecarboxylic Acid Derivatives

The present invention relates to novelpyridyloxy-phenoxyalkanecarboxylic acid derivatives which have aherbicidal and plant growth-regulating action, processes for theirproduction, compositions which contain these compounds as activeingredients, and to a method of selectively controlling weeds and ofregulating plant growth which comprises the use of the novel activesubstances or of compositions which contain them.

The active compounds of the present invention have the formula I##STR2## wherein A represents the cyano group, a radical -COB or a2-oxazoline radical which is unsubstituted or mono- or polysubstitutedby methyl,

B represents a radical --OR₃, --SR₃, --NR₄ R₅ or --O--N═C (C₁ -C₄alkyl)₂ Z and D each individually represent hydrogen, halogen, cyano,nitro, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

E represents halogen, trifluoromethyl, cyano or nitro,

R₁ represents hydrogen, C₁ -C₄ alkyl or C₂ -C₈ alkoxyalkyl, or C₁ -C₅alkoxycarbonyl

R₂ represents hydrogen or C₁ -C₄ alkyl,

R₃ represents hydrogen, ammonium or an alkali or alkaline earth metalcation, a benzyl or C₁ -C₄ alkylammonio group, whose alkyl radicals maybe substituted by hydroxyl C₁ -C₄ alkoxy or

a C₁ -C₁₈ alkyl radical which is unsubstituted or substituted byhalogen, cyano, C₁ -C₈ alkoxyalkoxy, C₂ -C₈ alkoxycarbonyl, bis(C₁ -C₄alkyl)amino, C₃ -C₈ cycloalkyl, C₃ -C₈ cycloalkenyl and also by a 5 to6-membered heterocyclic radical which is unsubstituted or is itselfmono- or polysubstituted by C₁ -C₄ alkyl;

a C₃ -C₁₀ alkenyl radical which is unsubstituted or mono- totetra-substituted by halogen;

a C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl- or C₃ -C₈ cycloalkenyl radical;

a phenyl or benzyl radical, which is mono- or polysubstituted byhalogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, nitro,trifluoromethyl, cyano, carboxyl, sulfonyl, hydroxyl, amino or bis(C₁-C₄ alkyl)amino;

a 5 to 6-membered heterocyclic radical;

R₄ represents hydrogen, a C₁ -C₈ alkyl radical, unsubstituted orsubstituted by halogen, hydroxyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄alkoxycarbonyl;

C₃ -C₈ alkenyl, unsubstituted or halogensubstituted;

C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl or C₃ -C₈ cycloalkenyl;

phenyl or benzyl, unsubstituted or substituted by halogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, trifluoromethyl, nitro or cyano;

R₅ represents the same as R₄ or C₁ -C₄ alkoxy or C₂ -C₄ alkenyloxy or R₄and R₅ together with the nitrogen atom, to which they are attached, formalso a 5 to 6-membered heterocyclic ring, which may be substituted by C₁-C₄ alkyl.

In the above formula the alkyl radicals can be branched or unbranchedand contain the indicated number of carbon atoms. The heterocyclicradicals R₃ include, furyl-, tetrahydrofuryl-, oxane-,thiophene-radicals and further, the same that are also found by thesymbols R₄ and R₅ with the nitrogen to which they are attached,pyrrolidine, pyridine, piperidine, morpholine, oxazoline or piperazine.These rings may be substituted by C₁ -C₄ alkyl radicals.

The active compounds of the formula (I) of the present invention possessa herbicidal action, especially in post-emergent application, and can beused as weed-killers in crops of mono- and dicotyledonous plants. Theyalso possess advantageous growth-regulating effects (growth inhibition).In particular, they inhibit the growth of dicotyledonous plants.Exemplary of the useful application of the compounds of the presentinvention are:

the reduction of the vegetative growth in soya and similar leguminosae,resulting in an increase in the yield of these plants;

the inhibition of the undesirable growth of suckers in tobacco plants,the leading shoots of which have been cut, thus promoting the formationof larger and finer leaves;

the inhibition of the growth of grass and dicotyledonous plants, such asfruit trees, ornamental trees, bushes and hedgerows, with the object ofsaving cutting work.

The compounds of the present invention have a low toxicity towarm-blooded animals and their application causes no problems. The rateof application is between 0.1 and 5 kg per hectare.

Good herbicidal activity has been observed with the groups of compoundslisted below. They are therefore of special interest among the compoundsof formula I. ##STR3##

In these formulae, B has the meanings given above under formula I.

From the U.S. Pat. Nos. 4,046,553 and 4,105,435 have become know4-pyridyloxy-phenoxyalkanecarboxylic acid derivatives with herbicidalactivity. The compounds of this invention proved to act differently andare capable of controlling plants, which were not or not satisfactorilycontrolled with compounds known from these patents.

The novel compounds of the formula (I) can be obtained by processeswhich are in themselves known. In a first process, a substituted orunsubstituted halopyridine of the formula II, ##STR4## wherein D and Eare as defined in formula (I) and Hal represents a halogen atom,preferably a chlorine or bromine atom, is reacted with ahydroxyphenoxyalkanecarboxylic acid derivative of the formula III,##STR5## wherein A, C, R₁ and R₂ are as defined in formula (I), in thepresence of an acid acceptor.

Such reactions are in themselves known and the exact method by whichthey are carried out is described in the literature, for example inHouben-Weyl, Volume 3, page 85 ff.

In a second process, the pyridyloxy-phenoxyalkanecarboxylic acidderivatives of the formula (I) are prepared by reacting apyridyloxy-hydroxyphenyl ether of the formula IV, ##STR6## wherein Z, Dand E are as defined in formula (I), with an α-halogenocarboxylic acidderivative of the formula V ##STR7## wherein A, R₁ and R₂ are as definedin formula (I) and Hal represents a halogen atom, preferably a chlorineor bromine atom, in the presence of an acid acceptor.

The above reactions can be carried out in the presence or absence ofsolvents or diluents which are intert to the reactants. Polar organicsolvents, such as methyl ethyl ketone, acetonitrile, dimethyl formamide,dimethyl sulphoxide etc., are preferred. The reaction temperatures arebetween 0° and 200° C. and the reaction time is from 1/4 hour to severaldays, depending on the chosen reaction temperature and solvent. Thereaction is ordinarily carried out under normal pressure or slightexcess pressure. Suitable acid acceptors for the reaction are inorganicbases, for example NaOH, KOH, NaOCH₃, NaH, K₂ CO₃, potassiumtert-butylate etc., and also organic bases.

A number of the starting materials of the formulae (II) to (V) areknown. Starting materials of these formulae which have not yet beendescribed can be easily prepared by conventional processes andtechniques.

Substituted 2-halogeno-pyridines of the formula (II) can be easilyobtained from the corresponding 2-pyridinoles, some of which are known.Starting materials of the formula (III) can be obtained by reacting, forexample, a monobenzyl ether of an optionally substituted resorcinol withan α-halogenocarboxylic acid derivative, preferably an ester of theformula (V), and cleaving the benzyl-phenyl ether bond by catalytichydrogenation, for example with a palladium on carbon catalyst, wherebythe benzyl radical is removed as toluene.

The starting materials of the formula (IV) can be obtained by reactionof resorcinol with halopyridines in equimolar amounts and in thepresence of a base.

Carboxylic acid derivatives of the formula (V) are also known. As theirsimplest representatives, mention may be made for example ofchloroacetic acid and the esters, thioesters and amides thereof.However, other α-halocarboxylic acid derivatives substituted inaccordance with R₁ and R₂ are also suitable.

The following Examples illustrate the process of the present inventionfor obtaining arbitrarily chosen active compounds of the formula (I).Further active compounds which are obtained in corresponding manner arelisted in the subsequent tables.

These pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula(I) are stable compounds which are soluble in conventional organicsolvents, such as alcohols, ethers, ketones, dimethyl formamide,dimethyl sulphoxide etc.

EXAMPLE 1 α-[3-(3',5'-Dichloropyrid-2-yl)-oxy-phenoxy]propionic acidmethyl ester (intermediate) ##STR8##

30.8 g (0.1 mole) of 3-(3',5'-dichloropyrid-2'-yl)-oxy-phenoxy phenol,18.2 g (0.13 mole) of potassium carbonate and 22 g of methylα-bromopropionate are refluxed in 300 ml of ethyl ketone for 3 hours.The inorganic salts are then filtered off and the filtrate isconcentrated. Recrystallization of the residue from ether/petroleumether affords 29 g (70% of theory) of the title product with a meltingpoint of 58°-60° C.

EXAMPLE 2 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy]propionicacid methyl ester ##STR9##

(a) 171 g (0.5 mole) ofα-[3-(3',5'-dichloropyrid-2-yl)oxy-phenoxy]propionic acid (preparedaccording to Example 1) are dissolved in 250 ml of 1,2 dichloroethane.The reaction is then cooled to -12° to -14° C. and during 2 hours thereis added dropwise 250 ml of 100% nitric acid. After 1/2 hour, thereaction mixture is poured into ice-water. The mixture is then extractedmethylene chloride. The organic phase is washed twice with water, driedover magnesium sulfate and evaporated. The residue is taken up in 500 mlof hexane and triturated, which causes it to crystallise. The cristalsare filtered and dried to yield 172.3 g (89% of theory) of the titlecompound which melts at 107°-108° C.

This compound can also be produced in the following manner.

(b) 30.1 g (0.1 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenol,16.7 g (0.1 mole) of methyl α-bromopropionate and 20.7 g (0.15 mole) ofpotassium carbonate are refluxed for 14 hours in 400 ml of methyl ethylketone. The inorganic salts are filtered off and the filtrate isconcentrated. The residual brown oil is taken up in chloroform andfiltered over a short column of silica gel, affording 22.4 g (58% oftheory) of title product which melts at 107° C. after recrystallisationfrom hexane.

EXAMPLE 3 3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenyl acetate(intermediate)

A mixture of 256 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.9liters of glacial acetic acid and 280 ml of acetic anhydride is stirredfor 12 hours at reflux temperature. The solution is cooled to 40° C.,then 81 g of sodium acetate are added with stirring and 106 g ofchlorine gas are introduced at 40° C. in the course of 7 hours. Excesschlorine gas is removed by introducing nitrogen for 2 hours and thesolution is concentrated. The ethyl acetate solution (1000 ml) of theoily residue is washed with water and saturated NaHCO₃ solution andconcentrated, affording 343 g of the title compound as a brown oil whichcrystallises spontaneously on trituration with petroleum ether.

Melting point: 71°-75° C.

EXAMPLE 4 3-(3',5'-Dichloropyridyl-2'-oxy)-6- and 4-chlorophenol(intermediate)

A suspension of 2.26 g of powdered KOH and 10 g of3-(3',5'-dichloropyridyl-2'-oxy)-6-phenyl acetate in 30 ml of absolutemethanol is stirred for 20 minutes at 60° C. in a nitrogen atmosphere,cooled to room temperature, acidified with 3.7 ml of concentratedhydrochloric acid and concentrated. The toluene solution (50 ml) of theresidue is washed with water, dried, filtered over activated carbon andconcentrated, affording 8.4 g of an oil which consists of a mixture ofthe 6-chlorophenol and 4-chlorophenol isomers in the ratio 7:3.

EXAMPLE 5 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy]propionicacid methyl ester ##STR10##

25 g (0.085 mole) of a mixture of3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenol and3-(3',5'-dichloropyridyl-2'-oxy)-4-chlorophenol (prepared according toExample 4), 14.2 g (0.085 mole) of methyl α-bromopropionate and 13.8 g(0.01 mole) of potassium carbonate are refluxed for 6 hours in 250 ml ofmethyl ethyl ketone. The inorganic salts are filtered off and thefiltrate is concentrated. The residual yellow oil is recrystallised fromether/petroleum ether, affording 30.1 g (94% of theory) if isomer-freetitle product with a melting point of 82°-83° C.

EXAMPLE 6 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenyl acetate(intermediate)

A mixture of 205 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.1liters of glacial acetic acid and 224 ml of acetic anhydride is stirredfor 12 hours at reflux temperature. The solution is cooled to 60° C.,then 64.8 g of sodium acetate are added with stirring and a solution of102 ml of bromine in 400 ml of glacial acetic acid are added dropwise at60° C. in the course of 53/4 hours. The solution is concentrated and theresidue is dissolved in ethyl acetate. The organic phase is washed insuccession with water and saturated NaHCO₃ solution. The combined ethylacetate extracts are dried and concentrated, affording 302.5 g of an oilwhich crystallises on being covered with a layer of petroleum ether(b.p. 60°-90° C.). After recrystallisation from cyclohexane, the titleproduct melts at 106°-107° C.

EXAMPLE 7 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenol (intermediate)

A suspension of 28 g of powdered KOH and 153.5 g of3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenyl acetate in one liter ofabsolute methanol is stirred for 20 minutes at 60° C. in a nitrogenatmosphere and concentrated. The concentrate is acidified at roomtemperature with concentrated hydrochloric acid and evaporated todryness. The toluene solution (400 ml) of the residue is washed withwater, dried, and concentrated. The oily residue is triturated withpetroleum ether/cyclohexane and filtered, affording 137 g of thecrystalline title product with a melting point of 93°-95° C.

EXAMPLE 8 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy]propionicacid methyl ester ##STR11##

50.2 g (0.15 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenol(prepared according to Example 7), 27.5 g (0.165 mole) of methylα-bromopropionated and 27.6 g (0.2 mole) of potassium carbonate arerefluxed for 5 hours in 250 ml of methyl ethyl ketone. The inorganicsalts are filtered off and the filtrate is concentrated. The residualreddish oil is recrystallised from ether/petroleum ether, affording 58 g(91.8% of theory) of the title compound with a melting point of 75° C.

Analogously to these Examples, the following compound can be prepared:

    ______________________________________                                         ##STR12##                                                                    No.       B                 phys. data                                        ______________________________________                                        1         OCH.sub.3         m.p. 82-83°                                2         OC.sub.2 H.sub.5  m.p. 53-56°                                3         OC.sub.3 H.sub.7 iso                                                                            n.sub.D.sup.25 1.5567                             4         OC.sub.3 H.sub.7 n                                                  5         OC.sub.4 H.sub.9 n                                                                              n.sub.D.sup.25 1.5540                             6         OC.sub.4 H.sub.9 sec.                                                                           n.sub.D.sup.25 1.5525                             7         OC.sub.4 H.sub.9 tert.                                              8         OC.sub.4 H.sub.9 iso                                                                            n.sub.D.sup.25 1.5538                             9         OCH(CH.sub.3)C.sub.3 H.sub.7 n                                      10        OCH(CH.sub.3)C.sub.5 H.sub.11 n                                     11        OC.sub.8 H.sub.17 n                                                 12        OC.sub.2 H.sub.4 OCH.sub.3                                                                      n.sub.D.sup.25 1.5547                             13        OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                   14        OC.sub.2 H.sub.4 Cl                                                                             n.sub.D.sup.25 1.5722                             15        OC.sub.2 H.sub.4 Br                                                 16                                                                                       ##STR13##        n.sub.D.sup.30 1.5617                             17                                                                                       ##STR14##                                                          18                                                                                       ##STR15##        n.sub.D.sup.30 1.5565                             19        OCH.sub.2 CHCH.sub.2                                                                            n.sub.D.sup.25 1.5629                             20        OC.sub.2 H.sub.4CHCH.sub.2                                          21        OCH.sub.2 C(CH.sub.3)CH.sub.2                                       22        OCH.sub.2 CCH     m.p. 64-68°                                23        OCH(CH.sub.3)CCH                                                    24                                                                                       ##STR16##                                                          25                                                                                       ##STR17##                                                          26        OCH.sub.2 CN                                                        27        OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                                             n.sub.D.sup.30 1.5445                             28        SCH.sub.3         n.sub.D.sup.25 1.5850                             29        SC.sub.2 H.sub.5                                                    30        SC.sub.3 H.sub.7 n                                                  31        SC.sub.3 H.sub.7 iso                                                32        SC.sub.4 H.sub.9 iso                                                33        SCH.sub.2 CHCH.sub.2                                                34        SCH.sub.2CHCHCH.sub.3                                               35        SCH.sub.2 COOCH.sub.3                                                                           n.sub.D.sup.40 1.5788                             36                                                                                       ##STR18##                                                          37        O.sup.⊖ Na.sup.⊕                                                                    m.p. 98-101                                       38        O.sup.⊖ NH.sub.4.sup.⊕                                  39        NH.sub.2          m.p. 142-5°                                40        N(CH.sub.3).sub.2                                                   41        NHC.sub.2 H.sub.5 m.p. 112-5°                                42        NHC.sub.2 H.sub.4 OH                                                43        NH(CH.sub.2).sub.3 OCH.sub.3                                                                    m.p. 90-92°                                44        NHC.sub.2 H.sub.4 OCH.sub.3                                                                     m.p. 89-91°                                45        NHC.sub.2 H.sub.4 Cl                                                46        NHCH.sub.2 CHCH.sub.2                                                                           m.p. 119-120°                              47        N(CH.sub.2 CHCH.sub.2).sub.2                                        48        NHC.sub.3 H.sub.7 iso                                               49        N(C.sub.2 H.sub.5).sub.2                                                                        m.p. 73-4°                                 50        NHC.sub.4 H.sub.9 n                                                 51        NHC.sub.5 H.sub.11 iso                                              52                                                                                       ##STR19##                                                          53                                                                                       ##STR20##        m.p. 39-42°                                54        NHCH.sub.2 COOC.sub.2 H.sub.5                                       55        N(CH.sub.3)OCH.sub.3                                                                            m.p. 75-7°                                 56        ONC(CH.sub.3)C.sub.2 H.sub.5                                        57        ONC(CH.sub.3).sub.2                                                 58                                                                                       ##STR21##                                                           ##STR22##                                                                    ______________________________________                                        59        OCH.sub.3                                                           60        OC.sub.2 H.sub.5                                                    61        OCH.sub.2CHCH.sub.2                                                 62        OC.sub.3 H.sub.6 OCH.sub.3                                          63        SCH.sub.3                                                           64        SCH.sub.2 CCH                                                       65        NHCH.sub.3                                                          66        N(CH.sub.3)OCH.sub.3                                                                            n.sub.D.sup.30 1.5613                              ##STR23##                                                                    ______________________________________                                        67        OCH.sub.3         m.p. 88-89°                                68        OC.sub.2 H.sub.5  n.sub.D.sup.30 1.5620                             69        OC.sub.3 H.sub.7 iso                                                                            n.sub.D.sup.30 1.5563                             70        OC.sub.4 H.sub.9 iso                                                71        OC.sub.2 H.sub.4 OCH.sub.3                                          72        OCH.sub.2 CN                                                        73        ONC(CH.sub.3).sub.2                                                 74        OCH.sub.2 COOCH.sub.3                                               75        SCH.sub.3                                                           76        SC.sub.3 H.sub.7 iso                                                77        SC.sub.5 H.sub.11 n                                                 78        NH.sub.2                                                            79        NHC.sub.2 H.sub.5 m.p. 104-5°                                80        N(C.sub.2 H.sub.5).sub.2                                            81        NHCH.sub.3                                                          82        NHCH.sub.2 CHCH.sub.2                                               83        NHCH.sub.2 CCH                                                      84        N(CH.sub.3)OCH.sub.3                                                                            n.sub.D.sup.25 1.5660                             85                                                                                       ##STR24##                                                          86                                                                                       ##STR25##                                                           ##STR26##                                                                    ______________________________________                                        87        OCH.sub.3         m.p. 107-8°                                88        OC.sub.2 H.sub.5                                                    89        OC.sub.3 H.sub.7 n                                                  90        OC.sub.3 H.sub.7 iso                                                                            n.sub.D.sup.30 1.5638                             91        OC.sub.4 H.sub.9 n                                                  92        OC.sub.4 H.sub.9 sec.                                                                           n.sub.D.sup.30 1.5630                             93        OCH(CH.sub.3)C.sub.4 H.sub.9 n                                      94        OC.sub.8 H.sub.17 n                                                 95        OC.sub.2 H.sub.4 OCH.sub.3                                                                      n.sub.D.sup.30 1.5709                             96        OCH(CH.sub.3)COOCH.sub.3                                            97        OC.sub.2 H.sub.4 Cl                                                 98        OCH.sub.2 CHCH.sub.2                                                                            n.sub.D.sup.30 1.5771                             99        OCH.sub.2 C(CH.sub.3)CH.sub.2                                       100       OCH.sub.2 C CH                                                      101                                                                                      ##STR27##                                                          102       OCH(CH.sub.3)CCH                                                    103       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                              n.sub.D.sup.40 1.5699                             104                                                                                      ##STR28##                                                          105                                                                                      ##STR29##                                                          106       SCH.sub.3                                                           107       SC.sub.2 H.sub.5                                                    108       SC.sub.4 H.sub.9 iso                                                109       SCH.sub.2 CHCH.sub.2                                                110       SCH.sub.2 C(CH.sub.3)CH.sub.2                                                                   n.sub.D.sup.30 1.5920                             111       SCH.sub.2 CCH     m.p. 92-95°                                112       NH.sub.2          m.p. 135-7°                                113       NHCH.sub.3        m.p. 126-7°                                114       N(CH.sub.3).sub.2 m.p. 116-7°                                115       NHC.sub.2 H.sub.5 m.p. 128-9°                                116       N(C.sub. 2 H.sub.5).sub.2                                                                       m.p. 88-9°                                 117       NHC.sub.3 H.sub.7 n                                                                             m.p. 112-4°                                118       NHC.sub.3 H.sub.7 iso                                                                           m.p. 112-3°                                119       NHCH.sub.2 CHCH.sub.2                                                                           m.p. 108-11°                               120       N(CH.sub.2 CHCH.sub.2).sub.2                                                                    n.sub.D.sup.30 1.5760                             121       NHCH.sub.2 CCH    m.p. 148-150°                              122       NHC.sub.4 H.sub.9 n                                                 123       NHC.sub.4 H.sub.9 sec.                                              124       NHC.sub.4 H.sub.9 iso                                               125       NHC.sub.5 H.sub.11 iso                                                                          m.p. 95-98°                                126       NHC.sub.6 H.sub.13 n                                                                            m.p. 87-90°                                127       NHC.sub.2 H.sub.4 OCH.sub.3                                                                     m.p. 101-3°                                128       NH(CH.sub.3)OCH.sub.3                                                                           m.p. 93-4°                                 129       NHC(CH.sub.3).sub.2 CCH                                                                         m.p. 118-120°                              130       NHCH.sub.2 COOC.sub.2 H.sub.5                                       131                                                                                      ##STR30##        m.p. 116-8°                                132                                                                                      ##STR31##        m.p. 118-120°                              133                                                                                      ##STR32##        m.p. 113-116°                              134                                                                                      ##STR33##        m.p. 132-134°                              135                                                                                      ##STR34##        m.p. 130-132°                              136                                                                                      ##STR35##                                                          137                                                                                      ##STR36##        m.p. 148-151°                              138                                                                                      ##STR37##        m.p. 134-137°                              139                                                                                      ##STR38##        m.p. 117-119°                              140       NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                  141       NHC.sub.3 H.sub.6 OCH.sub.3                                                                     n.sub.D.sup.40 1.5738                             142       NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                  143       NHC.sub.8 H.sub.17 n                                                144       OH                m.p. 134-6°                                145       O.sup.⊖ NH.sub.3 C.sub.3 H.sub.7 iso                        146       ONC(CH.sub.3).sub.2                                                  ##STR39##                                                                    ______________________________________                                        147       OH                                                                  148       OCH.sub.3         m.p. 80-2°                                 149       OC.sub.2 H.sub.5  n.sub.D.sup.25 1.5511                             150       OC.sub.3 H.sub.7 n                                                  151       OC.sub.3 H.sub.7 iso                                                                            n.sub.D.sup.30 1.5585                             152       OC.sub.4 H.sub.9 n                                                  153       OC.sub.4 H.sub.9 sec.                                                                           n.sub.D.sup.30 1.5590                             154       OC.sub.2 H.sub.4 Cl                                                 155       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                              n.sub.D.sup.30 1.5715                             156                                                                                      ##STR40##                                                          157       OC.sub.2 H.sub.4 OCH.sub.3                                          158       OC.sub.3 H.sub.6 OCH.sub.3                                          159       OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                 160       OCH.sub.2 CN                                                        161       OCH(CH.sub.3)COOC.sub.2 H.sub.5                                                                 n.sub.D.sup.30 1.5525                             162       ONC(CH.sub.3).sub.2                                                                             n.sub.D.sup.30 1.5665                             163       OCH.sub.2 CHCH.sub.2                                                                            n.sub.D.sup.30 1.5735                             164       OCH.sub.2 CHCHCH.sub.3                                              165       OCH(CH.sub.3)CHCH.sub.2                                             166       OCH.sub.2 CCH     n.sub.D.sup.30 1.5795                             167       OC(CH.sub.3).sub.2 CCH                                              168                                                                                      ##STR41##                                                          169                                                                                      ##STR42##                                                          170                                                                                      ##STR43##        m.p. 145-7°                                171                                                                                      ##STR44##                                                          172       SCH.sub.3         n.sub.D.sup.30 1.6015                             173       SC.sub.2 H.sub.5  n.sub.D.sup.30 1.5933                             174       SC.sub.4 H.sub.9 iso                                                175       SCH.sub.2 COOCH.sub.3                                               176       NH.sub.2          m.p. 156-9°                                177       NHCH.sub.3        m.p. 132-4°                                178       N(CH.sub.3).sub.2 m.p. 118-120°                              179       NHC.sub.2 H.sub.5                                                   180       N(C.sub.2 H.sub.5).sub.2                                            181       NHC.sub.3 H.sub.7 iso                                               182                                                                                      ##STR45##                                                          183       NHCH.sub.2 COOCH.sub.3                                              184                                                                                      ##STR46##                                                          185                                                                                      ##STR47##                                                          186       NHC.sub.2 H.sub.4 OCH.sub.3                                                                     m.p. 118-120°                              187       NHC.sub.3 H.sub.6 OCH.sub.3                                                                     m.p. 90-92°                                188       NHCH.sub.2 CHCH.sub.2                                                                           m.p. 104-6°                                189       N(CH.sub.2 CHCH.sub.2).sub.2                                        190       N(CH.sub.3)OCH.sub.3                                                                            n.sub.D.sup.30 1.5800                             191       NHOCH.sub.2 CHCH.sub.2                                               ##STR48##                                                                    ______________________________________                                        192       OCH.sub.3         m.p. 75°                                   193       OC.sub.2 H.sub.5                                                    194       OC.sub.3 H.sub.7 iso                                                                            m.p. 60-3°                                 195       OCH(CH.sub.3)C.sub.3 H.sub.7 n                                                                  n.sub.D.sup.30 1.5561                             196       OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                               n.sub.D.sup.30 1.5631                             197       OC.sub.2 H.sub.4 Cl                                                                             n.sub.D.sup.30 1.5792                             198       OC.sub.8 H.sub.17 n                                                                             n.sub.D.sup.30 1.5458                             199       OCH.sub.2 CHCHCH.sub.3                                                                          n.sub.D.sup.30 1.5730                             200       OCH.sub.2 CCH     m.p. 80-82°                                201                                                                                      ##STR49##        n.sub.D.sup.30 1.5811                             202       SC.sub.3 H.sub.7 iso                                                                            n.sub.D.sup.30 1.5795                             203       SC.sub.4 H.sub.9 iso                                                                            n.sub.D.sup.30 1.5805                             204       SCH.sub.2 COOCH.sub.3                                                                           n.sub.D.sup.30 1.5780                             205       SCH(CH.sub.3)C.sub.2 H.sub.5                                                                    n.sub.D.sup.30 1.5778                             206       NH.sub.2          m.p. 155-156°                              207       NHC.sub.2 H.sub.5 m.p. 114-115°                              208       N(CH.sub.3)OCH.sub.3                                                209       OH                m.p. 150-1°                                 ##STR50##                                                                    ______________________________________                                        210       OCH.sub.3         m.p. 74-77°                                211       OC.sub.2 H.sub.5                                                    212       OC.sub.3 H.sub.7 n                                                  213       OC.sub.3 H.sub.7 iso                                                214       OC.sub.4 H.sub.9 iso                                                215       OC.sub.6 H.sub.13 n                                                 216       OC.sub.2 H.sub.4 Cl                                                 217       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                  218       OC.sub.2 H.sub.4 OC.sub.4 H.sub.9                                   219                                                                                      ##STR51##                                                          220                                                                                      ##STR52##                                                          221                                                                                      ##STR53##                                                          222       OCH.sub.2 CHCH.sub.2                                                223       OCH(CH.sub.3)CHCH.sub.2                                             224       OCH.sub.2 CCH                                                       225       OCH(CH.sub.3)CCH                                                    226       SCH.sub.3                                                           227       SCH.sub.2 CHCH.sub.2                                                228       SCH(CH.sub.3)CHCH.sub.2                                             229       SCH.sub.2 CCH                                                       230                                                                                      ##STR54##                                                          231                                                                                      ##STR55##                                                          232       OH                                                                  233       O.sup.⊖ H.sub.3 N.sup.⊕ (C.sub.3 H.sub.7 iso).sub.2     234       O.sup.⊖ Na.sup.⊕                                        235       O.sup.⊖ NH.sub.4.sup.⊕                                  236       NH.sub.2                                                            237       NHCH.sub.3                                                          238       N(C.sub.2 H.sub.5).sub.2                                            239       NHC.sub.4 H.sub.9 iso                                               240       NHC.sub.2 H.sub.4 OCH.sub.3                                         241       NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                  242       N(CH.sub.3)OCH.sub.3                                                 ##STR56##                                                                    ______________________________________                                        243       OH                                                                  244       OCH.sub.3                                                           245       OC.sub.3 H.sub.7 iso                                                246       OC.sub.4 H.sub.9 n                                                  247       SCH.sub.3                                                           248       SCH.sub.2CHCH.sub.2                                                 249       SCH.sub.2 COOCH.sub.3                                               250       SC.sub.2 H.sub.4 OCH.sub.3                                          251       SC.sub.4 H.sub.9 iso                                                252                                                                                      ##STR57##                                                          253                                                                                      ##STR58##                                                          254       NH.sub.2                                                            255       NHC.sub.2 H.sub.5                                                   256       N(CH.sub.3).sub.2                                                   257       NHCH.sub.2 CHCH.sub.2                                               258       N(CH.sub.3)OCH.sub.3                                                259       NHC.sub.5 H.sub.11 n                                                 ##STR59##                                                                    ______________________________________                                        260       OH                                                                  261       OCH.sub.3         n.sub.D.sup.25 1.5150                             262       OC.sub.2 H.sub.5                                                    263       OC.sub.3 H.sub.7 n                                                  264       OC.sub.3 H.sub.7 iso                                                265       OCH.sub.2 CHCH.sub.2                                                266       OCH.sub.2 CCH                                                       267       OCH(CH.sub.3)COOC.sub.2 H.sub.5                                     268       NH.sub.2                                                            269       NHCH.sub.3                                                          270       N(CH.sub.3).sub.2                                                   271       N(C.sub.3 H.sub.7 iso).sub.2                                        272       NHCH.sub.2 CHCH.sub.2                                               273       NHCH.sub.2 CHCH                                                      ##STR60##                                                                    ______________________________________                                        274       OH                                                                  275       OCH.sub.3         m.p. 74-75°                                276       OC.sub.2 H.sub.5                                                    277       OCH.sub.2 CN                                                        278       OC.sub.3 H.sub.7 n                                                  279       OC.sub.3 H.sub.7 iso                                                280       OC.sub.4 H.sub.9 n                                                  281       OCH.sub.2 CHCH.sub.2                                                282       OCH.sub.2 CHCHCH.sub.3                                              283       OCH.sub.2 CCH                                                       284       SCH.sub.3                                                           285       SC.sub.2 H.sub.5                                                    286       SC.sub.3 H.sub.7 iso                                                287       SCH.sub.2 CN                                                        288       SCH.sub.2 COOCH.sub.3                                               289       NH.sub.2                                                            290       NHCH.sub.3                                                          291       N(CH.sub.3).sub.2                                                   292       NH(C.sub.3 H.sub.7 iso)                                             293       NHCH.sub.2 CHCH.sub.2                                               294                                                                                      ##STR61##                                                           ##STR62##                                                                    ______________________________________                                        295       OH                                                                  296       OCH.sub.3                                                           297       OC.sub.2 H.sub.5  n.sub.D.sup.30 1.5223                             298       OC.sub.3 H.sub.7 n                                                  299       OC.sub.4 H.sub.9 iso                                                300       OCH.sub.2 CHCH.sub.2                                                301       OCH.sub.2 CCH                                                       302       OCH(CH.sub.3)CCH                                                    303       OC.sub.4 H.sub.9 n                                                  304       OC.sub.4 H.sub.9 tert.                                              305       OC.sub.4 H.sub.9 sec.                                               306       OC.sub.2 H.sub.4 OCH.sub.3                                          307       OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                 308       OC.sub.2 H.sub.4 Cl                                                 309       OC.sub.2 H.sub.4 Br                                                 310       OCH.sub.2 CHCHCH.sub.2 Cl                                           311       OCH.sub.2 C(CH.sub.3)CH.sub.2                                       312       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                  313       OC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2                           314       OCH(CH.sub.3)COOC.sub.2 H.sub.5                                     315       OCH(C.sub.2 H.sub.5).sub.2                                          316       SH                                                                  317       SCH.sub.3                                                           318       SC.sub.2 H.sub.5                                                    319       SCH.sub.2 COOC.sub.2 H.sub.5                                        320       SCH.sub.2 CHCH.sub.2                                                321       SCH.sub.2 CCH                                                       322       SC.sub.4 H.sub.9 n                                                  323       SCH.sub.2CH(CH.sub.3)CH.sub.2                                       324       SCH(CH.sub.3)CCH                                                    325       NH.sub.2          m.p. 127-128°                              326       NHC.sub.2 H.sub.4 OCH.sub.3                                         327       NHC.sub.3 H.sub.6 OCH.sub.3                                         328       N(C.sub.2 H.sub.4 OH).sub.2                                         329       NHC.sub.2 H.sub.4 COOCH.sub.3                                       330       NHCH.sub.2 COOCH.sub.3                                              331       NHC.sub.2 H.sub.4 OH                                                332       NHCH.sub.3        m.p. 113-114°                              333       N(CH.sub.3).sub.2                                                   334       NHC.sub.2 H.sub.5                                                   335       N(C.sub.2 H.sub.5).sub.2                                            336       NHC.sub.3 H.sub.7 n                                                 337       NHC.sub.4 H.sub.9 n                                                 338                                                                                      ##STR63##                                                          339       N(CH.sub.3)OCH.sub.3                                                 ##STR64##                                                                    ______________________________________                                        340       OH                                                                  341       OCH.sub.3         m.p. 89-93°                                342       OC.sub.2 H.sub.5  n.sub.D.sup.20 1.5340                             343       OCH.sub.2 CHCH.sub.2                                                344       SCH.sub.2 CHCH.sub.2                                                345       SCH.sub.3                                                           346       SCH.sub.2 COOCH.sub.3                                               347       NH.sub.2                                                            348       NHCH.sub.3                                                          349       N(CH.sub.3).sub.2                                                   350       NHC.sub.2 H.sub.5                                                   351       NHCH.sub.2 CHCH.sub.2                                                ##STR65##                                                                    ______________________________________                                        352       OH                                                                  353       OCH.sub.3                                                           354       OC.sub.2 H.sub.5  n.sub.D.sup.30 1.5167                             355       OC.sub.3 H.sub.7 iso                                                356       OC.sub.2 H.sub.4 OCH.sub.3                                          357       OCH.sub.2 CHCH.sub.2                                                358       OCH.sub.2CH                                                         359       SCH.sub.3                                                           360       SC.sub.2 H.sub.5                                                    361       SCH.sub.2 CHCH.sub.2                                                362       NH.sub.2                                                            363       N(CH.sub.3).sub.2                                                   364       NHC.sub.2 H.sub.5                                                   365       NHC.sub.2 H.sub.4 OCH.sub.3                                         366       N(CH.sub.3)OCH.sub.3                                                ______________________________________                                         ##STR66##                                                                    No.   E      D      Z    B          phys. data                                ______________________________________                                        367   Cl     Br     Cl   OCH.sub.3                                            368   Cl     Br     Cl   OC.sub.2 H.sub.5                                     369   I      H      NO.sub.2                                                                           OCH.sub.3  n.sub.D.sup.25 1.6125                     370   I      H      Cl   OCH.sub.3  n.sub.D.sup.25 1.5995                     371   Br     Br     NO.sub.2                                                                           OCH.sub.3  m.p. 118-120°                      372   CN     Cl     Cl   OCH.sub.3  m.p. 109-111°                      373   Br     CN     Cl   OCH.sub.3  m.p. 135-7°                        374   Cl     H      Cl   OCH.sub.3  b.p. 145-150°/0.04                 375   Cl     H      NO.sub.2                                                                           NH.sub.2                                             376   Br     H      NO.sub.2                                                                           OC.sub.2 H.sub.5                                     377   Br     H      Cl   OCH.sub.2 CHCH.sub.2                                 378   CN     Cl     Br   OCH.sub.3  m.p. 107-9°                        379   CF.sub.3                                                                             Cl     Br   OCH.sub.3                                            380   Cl     CH.sub.3                                                                             Cl   OCH.sub.3                                            381   Cl     CH.sub.3                                                                             Br   OC.sub.2 H.sub.5                                     382   Cl     CH.sub.3                                                                             NO.sub.2                                                                           OCH.sub.3                                            383   Cl     CH.sub.3                                                                             NO.sub.2                                                                           NHCH.sub.3                                           384   CF.sub.3                                                                             H      Br   OCH.sub.3                                            385   CF.sub.3                                                                             Br     Cl   OCH.sub.3                                            386   Br     Br     Br   OCH.sub.3  m.p. 64-6°                         387   Br     Br     NO.sub.2                                                                           OCH.sub.3  m.p. 118-120°                      388   Br     Br     Br   SCH.sub.3                                            389   Br     Br     Cl   OCH.sub.3  m.p. 86-8°                         390   Cl     H      Br   OCH.sub.3  m.p. 80-2°                         391   CF.sub.3                                                                             Br     NO.sub.2                                                                           NH.sub.2                                             392   CF.sub.3                                                                             Br     NO.sub.2                                                                           NHCH.sub.3                                            ##STR67##                                                                    ______________________________________                                        393   Cl     Br     NO.sub.2                                                                           OC.sub.2 H.sub.5                                                                         n.sub.D.sup.25 1.5820                     394   CN     Cl     NO.sub.2                                                                           OC.sub.2 H.sub.5                                     395   Cl     CH.sub.3                                                                             NO.sub.2                                                                           OC.sub.2 H.sub.5                                     396   Cl     CH.sub.3                                                                             NO.sub.2                                                                           NH.sub.2                                             397   Br     Br     NO.sub.2                                                                           OC.sub.2 H.sub.5                                     398   CF.sub.3                                                                             Br     NO.sub.2                                                                           OC.sub.2 H.sub.5                                      ##STR68##                                                                    ______________________________________                                        399   Cl     Cl     NO.sub.2                                                                           OCH.sub.3  m.p. 83-5°                         400   Cl     Cl     NO.sub.2                                                                           NH.sub.2   m.p. 203-5°                        401   Cl     Cl     NO.sub.2                                                                           NHC.sub.2 H.sub.5                                                                        m.p. 124-5°                        402   Cl     Cl     NO.sub.2                                                                           N(CH.sub.3)OCH.sub.3                                                                     m.p. 106-7°                        403   Cl     Cl     NO.sub.2                                                                           OC.sub.2 H.sub.4 OCH.sub.3                                                               m.p. 71-2°                         404   Cl     Cl     Br   OCH.sub.3  m.p. 81-2°                         405   Cl     CH.sub.3                                                                             NO.sub.2                                                                           OCH.sub.3                                            406   CF.sub.3                                                                             Cl     NO.sub.2                                                                           OCH.sub.3                                            407   CF.sub.3                                                                             H      NO.sub.2                                                                           OCH.sub.2 CHCH.sub.2                                 408   CF.sub.3                                                                             H      Cl   OCH.sub.3                                            409   CF.sub.3                                                                             Cl     Cl   OCH.sub.3                                             ##STR69##                                                                    ______________________________________                                        410   Cl     Cl     Cl   OCH.sub.3  n.sub.D.sup.30 1.5586                     411   Cl     Cl     NO.sub.2                                                                           OCH.sub.3  n.sub.D.sup.30 1.5527                     412   Cl     Cl     NO.sub.2                                                                           OC.sub.2 H.sub.5                                     413   Cl     Cl     NO.sub.2                                                                           NHCH.sub.3                                           414   CF.sub.3                                                                             H      NO.sub.2                                                                           OCH.sub.3                                            415   CF.sub.3                                                                             Cl     NO.sub.2                                                                           OC.sub.2 H.sub.5                                     416   CF.sub.3                                                                             Cl     Cl   OCH.sub.3                                            417   Br     Br     NO.sub.2                                                                           OCH.sub.3                                            ______________________________________                                         ##STR70##                                                                    No.       B                 phys. data                                        ______________________________________                                        418       OCH.sub.3         m.p. 93-94°                                419       OC.sub.2 H.sub.5                                                    420       OC.sub.2 H.sub.4 OCH.sub.3                                          421       NH.sub.2          m.p. 145-146°                              422       NHCH.sub.3        m.p. 132-134°                              423       N(CH.sub.3).sub.2 m.p. 136-137°                              424       NHC.sub.2 H.sub.5 m.p. 124-126°                              425       N(C.sub.2 H.sub.5).sub.2                                                                        m.p. 75-77°                                ______________________________________                                         ##STR71##                                                                    No.   E     D      Z    R.sub.1                                                                            A          phys. data                            ______________________________________                                        426   Cl    Cl     NO.sub.2                                                                           H    CN         m.p. 118-120°                  427   Cl    Cl     Cl   CH.sub.3                                                                           CN         m.p. 119-120°                  428   Cl    Cl     Cl   H    CN         m.p. 101-3°                    429   Cl    Cl     Cl   CH.sub.3                                                                            ##STR72## m.p. 133-5°                    430   Cl    Cl     Cl   CH.sub.3                                                                            ##STR73##                                       431   Cl    Cl     NO.sub.2                                                                           CH.sub.3                                                                            ##STR74##                                       ______________________________________                                    

The compositions of the present invention are obtained in known mannerby homogeneously mixing and grinding active substances of the generalformula I with suitable carriers, with or without the addition ofdispersants or solvents which are inert to the active substances. Theactive substances can be processed to the following formulations:

solid formulations: dusts, tracking powders, granules (coated granules,impregnated granules and homogeneous granules);

active substance concentrates which are dispersible in water: wettablepowders, pastes, emulsions;

liquid formulations: solutions.

The concentration of active substance in the above describedcompositions is between 0.1 and 95%, preferably between 1 and 80%. Therates of application are ordinarily from 0.1 to 10 kg, preferably from0.25 to 5 kg, of active substance per hectare. The compositions of thepresent invention can also be mixed with other biocidal activesubstances or compositions.

The active substances of the formula I can be formulated for example asfollows (parts are by weight):

Dusts: The following substances are used to prepare (a) 5% and (b) a 2%dust:

(a)

5 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy]propionicacid methyl ester,

95 parts of talc;

(b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground.

Granulate: The following substances are used to prepare a 5% granulate:

5 parts of the above active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.25 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture isdissolved in 6 parts of acetone. Then polyethylene glycol and cetylpolyglycol ether are added. The resulting solution is sprayed on kaolinand subsequently evaporated in vacuo.

Wettable Powders: The following constituents are used to prepare (a) a50%, (b) a 25% and (c) a 10% wettable powder:

(a)

50 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenoxy]propionicacid methyl ester

5 parts of sodium dibutylnaphthylsulphonate

3 parts of naphthalenesulfonic acid/phenolsulphonic acid/formaldehydecondensate (3:2:1)

20 parts of kaolin

22 parts of Champagne chalk;

(b)

25 parts of the above active substance

5 parts of sodium oleylmethyltauride

2.5 parts of naphthalenesulphonic acid/formaldehyde condensate

0.5 parts of carboxymethyl cellulose

5 parts of neutral potassium aluminium silicate

62 parts of kaolin;

(c)

10 parts of the above active substance

3 parts of a mixture of the sodium salts of saturated fatty alcoholsulphates

5 parts of naphthalenesulphonic acid/formaldehyde condensate

82 parts of kaolin.

The indicated active substance is applied to the corresponding carriers(kaolin and chalk) and then these are mixed and ground, to yieldwettable powders of excellent wettability and suspension power. Bydiluting these wettable powders with water it is possible to obtainsuspensions of the desired concentration of active substance. Suchsuspensions are used for controlling weeds and grass-like weeds in cropsof cultivated plants by the preemergent method and for treating areas ofgrass.

Paste: The following substances are used to manufacture a 45% paste:

45 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenoxy]propionicacid methyl ester

5 parts of sodium aluminium silicate

14 parts of cetyl polyglycol ether with 8 moles of the ethylene oxide

1 part of oleyl polyglycol ether with 5 moles of the ethylene oxide

2 parts of spindle oil

10 parts of polyethylene glycol

23 parts of water.

The active substance is homogeneously mixed with the adjuvants inappropriate devices and ground, yielding a paste from which, by dilutionwith water, it is possible to obtain suspensions of the desiredconcentration of active substance. The suspensions are suitable fortreating areas of grass.

Emulsifiable Concentrate: The following ingredients are mixed tomanufacture a 25% emulsifiable concentrate:

25 parts ofα-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy]propionic acidisopropyl ester

5 parts of a mixture of nonylphenolpolyoxyethoxy-ethylene and calciumdodecylenesulphonate

35 parts of 3,3,5-trimethyl-2-cyclohexan-1-one

35 parts of dimethyl formamide.

This concentrate can be diluted with water to give emulsions in thedesired concentrations.

Instead of using the respective active substance indicated in theforegoing formulation examples, it is also possible to use another ofthe compounds comprised by the formula I.

The active substances of the invention are also of interest forcombination with an number of hercides of the phenylurea and triazineseries for use in cereal crops, maize, sugar cane, and in fruit cultureand viticulture.

The active substances of the formula I are distinguished by a verypronounced preemergent herbicidal action and are thus also stronggermination inhibitors.

The following test methods were emloyed to established the usefulness ofthe compounds of the formula I as herbicides (pre- and postemergent).

Preemergent herbicidal action (germination inhibition)

In a greenhouse, immediately after sowing the test plants in seed dishesthe surface of the soil is treated with an aqueous suspension of theactive substances obtained from a 25% wettable powder. A concentrationwas used, which corresponded to 4 kg of active substance per hectare.The seed dishes are then kept in the greenhouse at 22°-25° C. and 50 to70% relative humidity. The test was evaluated 3 weeks later according tothe following rating:

1=plants have not germinated or are totally withered

2-8=intermediate stages of damage

9=plants undamaged (as untreated control).

The results are resumed in the table below:

    ______________________________________                                        Compound          Sinapis    Setaria                                                                             Stellaria                                  number     oats   alba       italica                                                                             media                                      ______________________________________                                         2         8      3          2     2                                           14        9      2          2     3                                           35        9      4          1     2                                           53        7      3          2     2                                           87        2      1          1     3                                          112        2      1          1     1                                          114        1      2          1     2                                          115        1      1          1     1                                          127        2      2          1     2                                          144        9      1          1     5                                          149        7      2          2     2                                          192        9      2          1     1                                          201        9      4          1     1                                          210        2      1          1     1                                          261        2      2          1     7                                          297        1      1          1     1                                          399        3      1          3     9                                          418        9      1          1     1                                          ______________________________________                                    

Post-emergent herbicidal action (Contact herbicide)

A number of weeds and cultivated plants, both mono- and dicotyledonous,were sprayed after emergence in the 4- to 6-leaf stage with an aqueousactive substance emulsion in a rate of 4 kg of active substance perhectare and kept at 24°-26° C. and 45-60% relative humidity. The testwas evaluated, as in the preemergent test, 15 days after treatment inaccordance with the same rating.

The results are resumed in the table below:

    ______________________________________                                        Compound        Setaria Lolium  Sinapis                                                                             Stellaria                               No.     oats    italica perenne alba  media                                   ______________________________________                                        1       2       1       1       1     1                                       2       4       1       2       1     1                                       3       4       1       3       2     2                                       12      7       1       3       1     2                                       16      6       2       3       1     2                                       19      5       1       3       1     2                                       22      6       2       6       2     1                                       27      4       1       2       1     1                                       28      6       1       5       3     2                                       35      5       1       3       1     1                                       41      4       5       4       2     2                                       43      4       1       4       1     1                                       53      5       2       6       1     2                                       55      6       1       3       1     1                                       66      4       1       4       2     3                                       92      2       1       1       1     3                                       95      4       2       3       1     6                                       98      4       1       1       1     2                                       111     4       2       2       1     2                                       113     2       2       2       2     3                                       115     2       2       5       1     5                                       128     2       1       3       1     1                                       129     7       1       6       1     6                                       141     4       3       4       1     4                                       149     2       1       2       1     1                                       192     3       1       1       1     1                                       194     3       1       1       1     1                                       196     3       1       1       1     1                                       200     4       1       2       1     1                                       201     7       1       3       1     1                                       202     6       2       4       2     2                                       204     5       2       3       2     2                                       210     1       1       1       1     1                                       261     1       1       1       1     1                                       297     1       1       1       1     1                                       372     4       2       4       2     1                                       387     2       1       1       1     1                                       399     1       1       2       1     3                                       403     2       1       2       1     8                                       418     4       1       2       1     4                                       426     2       1       3       1     4                                       ______________________________________                                    

We claim:
 1. A compound of the formula: ##STR75## wherein R₁ is methyl,ethyl or methoxymethyl,R₃ is alkyl of 1 to 5 carbon atoms, alkenyl of 3to 4 carbon atoms, propynyl, phenyl, or --CH₂ COOCH₃, and Z is chloro,bromo or nitro.
 2. A compound according to claim 1 wherein R₁ ismethoxymethyl.
 3. A compound according to claim 1 wherein R₁ is ethyl.4. A compound according to claim 3 wherein Z is nitro and R₃ is methyl.5. A compound according to claim 3 wherein Z is nitro and R₃ is ethyl.6. A compound according to claim 1 wherein R₁ is methyl.
 7. The compoundaccording to claim 6 wherein Z is chloro and R₃ is --CH₂ COOCH₃.
 8. Thecompound according to claim 6 wherein Z is chloro and R₃ is --CH₂C.tbd.CH.
 9. The compound according to claim 6 wherein Z is chloro andR₃ is --CH₂ C(CH₃)═CH₂.
 10. The compound according to claim 6 wherein Zis chloro and R₃ is methyl.
 11. The compound according to claim 6wherein Z is chloro and R₃ is isopropyl.
 12. The compound according toclaim 6 wherein Z is nitro and R₃ is --CH₃ COOCH₃.
 13. The compoundaccording to claim 6 wherein Z is nitro and R₃ is --CH₂ C.tbd.CH. 14.The compound according to claim 6 wherein Z is nitro and R₃ is --CH₂C(CH₃)═CH₂.
 15. The compound according to claim 6 wherein Z is nitro andR₃ is methyl.
 16. The compound according to claim 6 wherein Z is nitroand R₃ is isopropyl.
 17. The compound according to claim 6 wherein Z isbromo and R₃ is --CH₂ COOCH₃.
 18. The compound according to claim 6wherein Z is bromo and R₃ is isopropyl.
 19. A compound according toclaim 6 wherein Z is bromo and R₄ is isobutyl or sec. butyl.
 20. Aherbicidal composition which contains as active ingredient aherbicidally effective amount of a compound according to claim 1together with an inert carrier.
 21. A method for controlling weed at alocus, which comprises applying to said locus a herbicidally effectiveamount of a compound according to claim 1.